Impact modifier composition, an impact resistant composition, method of producing the same, and articles made therefrom

ABSTRACT

The instant invention is an impact modifier composition, an impact resistant composition, method of producing the same, and articles made therefrom. The impact modifier composition comprises (a) less than 30 percent by weight of high-density polyethylene, based on the weight of the impact modifier composition; and (b) at least 70 percent by weight of chlorinated polyethylene, based on the weight of the impact modifier composition. The impact resistant composition comprises (1) at least 85 percent by weight of poly(vinyl chloride), based on the weight of the impact resistant composition; and (2) less than 10 percent by weight of an impact modifier composition, based on the weight of the impact resistant composition, comprising; (a) less than 30 percent by weight of high-density polyethylene, based on the weight of the impact modifier composition; and (b) at least 70 percent by weight of chlorinated polyethylene, based on the weight of the impact modifier composition; wherein the impact resistant composition has an instrumented dart drop impact of greater than 0.90 inch-pounds per mil at −10° C.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a non-provisional application claiming priority fromthe U.S. Provisional Patent Application No. 60/990,927, filed on Nov.29, 2007, entitled “IMPACT MODIFIER COMPOSITION, AN IMPACT RESISTANTCOMPOSITION, METHOD OF PRODUCING THE SAME, AND ARTICLES MADE THEREFROM,”the teachings of which are incorporated by reference herein, as ifreproduced in full hereinbelow.

FIELD OF INVENTION

The instant invention relates to an impact modifier composition, animpact resistant composition, method of producing the same, and articlesmade therefrom.

BACKGROUND OF THE INVENTION

The use of poly(vinyl chloride) (“PVC”) both in its rigid form andflexible form as films, sidings, sheets, pipes, and tubing is generallywell known. Rigid PVC is a hard and brittle thermoplastic polymer thatis typically mixed with a modifier to form a composition that is lessprone to failure on impact.

Many modifications to poly(vinyl chloride) have been made to transformhard poly(vinyl chloride) into a softer, less brittle material. Theseprocesses are generally divided into external plasticizing processes,which are carried out by means of innumerable plasticizers known,recommended and used for these purposes and by internal plasticizing,wherein various other polymers are blended or combined with poly(vinylchloride) homopolymers or copolymers. Whichever method is carried out,considerable disadvantages have remained. For example, when usingexternal plasticizers, the extractability and tendency of theplasticizer to travel has been pronounced, in addition to a generaldecrease in either weathering or heat-aging characteristics ofpoly(vinyl chloride). When using internal plasticizers such ascopolymers, the advantages obtained by using such materials oftenentails the loss of dimensional stability and the like.

One particular disadvantage of PVC which has long been known is theextreme brittleness of the unmodified material. It has long been knownto modify PVC by adding high polymeric natural and synthetic substances.For example, vinyl chloride polymers are frequently plasticized withplasticizers which can migrate from the composition with age,particularly at elevated temperatures.

U.S. Pat. No. 3,006,889 describes the use of a blend of post-chlorinatedpolyvinylchloride, chlorinated polyethylene and chlorosulfonatedpolyethylene.

U.S. Pat. No. 3,209,055 describes polymeric blends of vinyl chloridepolymer with chlorinated or chlorosulfonated polyethylene which arecross-linked to improve resistance to heat distortion.

U.S. Pat. No. 3,396,211 describes compositions of vinyl chloride andrandomly chlorinated polyethylene as an impact modifier for rigidpoly(vinyl chloride) compositions.

U.S. Pat. No. 3,459,591 describes the method of producing heat sealablegas and vapor impermeable films by applying a coating on at least onesurface of the film comprising a homopolymer or copolymer of vinylidenechloride or vinyl chloride together with a chlorinated orchlorosulfonated polyolefin having a crystalline structure.

U.S. Pat. No. 4,280,940 describes transparent thermoplastic compositionson the basis of vinyl chloride polymers consisting of a mixture of aspecial vinyl chloride polymer and two different, differentlychlorinated chloropolyethylenes.

U.S. Pat. No. 4,767,823 describes halogenated ethylene polymers having areduced tendency to block. The halogenated resins are prepared frompolyethylene and ethylene polymer starting materials which have aweight-based median particle size of from about 120 to about 600 micronsand a weight-based particle size distribution such that more than 60percent of the particles have a particle size of from about 130 to about850 microns. The halogenated resins also have a weight-based medianparticle size of from about 200 to about 900 microns. The halogenatedpolyethylene resins have a chemically combined halogen content of fromabout 26 to about 42 weight percent whereas the halogenated ethylenepolymer resins have a chemically combined halogen content of from about15 to about 28 weight percent. The halogenated ethylene polymer resinsare prepared from ethylene polymer starting materials which havepolymerized therein up to five weight percent of 1-olefin monomercopolymerizable with ethylene.

U.S. Pat. No. 6,875,820 describes a chlorinated polyolefin impactmodifier for vinyl chloride polymers. The chlorinated olefin impactmodifier is prepared from an olefin polymer base resin having I₁₀ valuesof 0.05 to 0.8 g/10 minute.

German Pat. No. 1,111,383 describes a high impact molding compositionbased on post-chlorinated vinyl chloride copolymers produced by adding10 to 50 percent of chlorinated and/or chlorosulfonated products of highpolymeric aliphatic hydrocarbons such as polyethylene to the postchlorinated polymers.

Japan Kokai 56-17255 describes manufacturing products coated with flameretarding chlorinated rubber comprising 15 to 80 weight percent chlorinesuch as chlorinated polyethylene, chlorosulfonated polyethylene and PVC.

Despite the research efforts in developing poly(vinyl chloride)compositions having improved low temperature impact properties, there isstill a need for a poly(vinyl chloride) composition having improved lowtemperature impact properties at optimum efficiency.

SUMMARY OF THE INVENTION

The instant invention is an impact modifier composition, an impactresistant composition, method of producing the same, and articles madetherefrom. The impact modifier composition comprises (a) less than 30percent by weight of high-density polyethylene, based on the weight ofthe impact modifier composition; and (b) at least 70 percent by weightof chlorinated polyethylene, based on the weight of the impact modifiercomposition. The method for producing the impact modifier compositioncomprises the steps of (1) selecting high-density polyethylene in apowder form; (2) selecting chlorinated polyethylene in a powder form;(3) uniformly admixing said high-density polyethylene and saidchlorinated polyethylene; and (4) thereby producing said impact modifiercomposition, wherein said impact modifier composition comprises (a) lessthan 30 percent by weight of high-density polyethylene based on thetotal weight of the impact modifier composition, based on the weight ofimpact modifier composition; and (b) at least 70 percent by weight ofchlorinated polyethylene, based on the weight of the impact modifiercomposition. The impact resistant composition comprises (1) at least 85percent by weight of poly(vinyl chloride), based on the weight of theimpact resistant composition; and (2) less than 10 percent by weight ofan impact modifier composition, based on the weight of the impactresistant composition, comprising; (a) less than 30 percent by weight ofhigh-density polyethylene, based on the weight of the impact modifiercomposition; and (b) at least 70 percent by weight of chlorinatedpolyethylene, based on the weight of the impact modifier composition;wherein the impact resistant composition has an instrumented dart dropimpact of greater than 0.90 inch-pounds per mil at −10° C. The methodfor producing the impact resistant composition comprises the steps of(1) selecting poly(vinyl chloride); (2) selecting an impact modifiercomposition comprising; (a) less than 30 percent by weight ofhigh-density polyethylene, based on the weight of the impact modifiercomposition; and (b) at least 70 percent by weight of chlorinatedpolyethylene, based on the weight of the impact modifier composition;(3) melt blending the poly(vinyl chloride) and the impact modifiercomposition; and (4) thereby producing the impact resistant compositioncomprising at least 85 percent by weight of poly(vinyl chloride), basedon the weight of the impact resistant composition; and (2) less than 10percent by weight of the impact modifier composition. The articlecomprises (1) at least 85 percent by weight of poly(vinyl chloride),based on the weight of the impact resistant composition; and (2) lessthan 10 percent by weight of an impact modifier composition, based onthe weight of the impact resistant composition, comprising; (a) lessthan 30 percent by weight of high-density polyethylene, based on theweight of the impact modifier composition; and (b) at least 70 percentby weight of chlorinated polyethylene, based on the weight of the impactmodifier composition; wherein the article has an instrumented dart dropimpact of greater than 0.90 inch-pounds per mil at −10° C.

In one embodiment, the instant invention provides an impact modifiercomposition comprising (a) less than 30 percent by weight ofhigh-density polyethylene, based on the weight of the impact modifiercomposition; and (b) at least 70 percent by weight of chlorinatedpolyethylene, based on the weight of the impact modifier composition.

In an alternative embodiment, the instant invention further provides animpact resistant composition comprising (I) at least 85 percent byweight of poly(vinyl chloride), based on the weight of the impactresistant composition; and (2) less than 10 percent by weight of animpact modifier composition, based on the weight of the impact resistantcomposition, comprising; (a) less than 30 percent by weight ofhigh-density polyethylene, based on the weight of the impact modifiercomposition; and (b) at least 70 percent by weight of chlorinatedpolyethylene, based on the weight of the impact modifier composition;wherein the impact resistant composition has an instrumented dart dropimpact of greater than 0.90 inch-pounds per mil at −10° C.

In an alternative embodiment, the instant invention further provides animpact resistant composition comprising the melt blending product of (1)at least 85 percent by weight of poly(vinyl chloride), based on theweight of the impact resistant composition; and (2) less than 10 percentby weight of an impact modifier composition, based on the weight of theimpact resistant composition, comprising; (a) less than 30 percent byweight of high-density polyethylene, based on the weight of the impactmodifier composition; and (b) at least 70 percent by weight ofchlorinated polyethylene, based on the weight of the impact modifiercomposition; wherein the impact resistant composition has aninstrumented dart drop impact of greater than 0.90 inch-pounds per milat −10° C.

In an alternative embodiment, the instant invention further provides amethod for producing an impact modifier composition comprising the stepsof (1) selecting high-density polyethylene in a powder form; (2)selecting chlorinated polyethylene in a powder form; (3) uniformlyadmixing said high-density polyethylene and said chlorinatedpolyethylene; and (4) thereby producing said impact modifiercomposition, wherein said impact modifier composition comprises (a) lessthan 30 percent by weight of high-density polyethylene, based on theweight of the impact modifier composition; and (b) at least 70 percentby weight of chlorinated polyethylene, based on the weight of the impactmodifier composition.

In an alternative embodiment, the instant invention further provides amethod for producing an impact resistant composition comprising thesteps of (1) selecting poly(vinyl chloride); (2) selecting an impactmodifier composition comprising; (a) less than 30 percent by weight ofhigh-density polyethylene, based on the weight of the impact modifiercomposition; and (b) at least 70 percent by weight of chlorinatedpolyethylene, based on the weight of the impact modifier composition;(3) melt blending the poly(vinyl chloride) and the impact modifiercomposition; and (4) thereby producing the impact resistant compositioncomprising at least 85 percent by weight of poly(vinyl chloride), basedon the weight of the impact resistant composition; and (2) less than 10percent by weight of an impact modifier composition, based on the weightof the impact resistant composition.

In another alternative embodiment, the instant invention furtherprovides an article comprising (1) at least 85 percent by weight ofpoly(vinyl chloride), based on the weight of the impact resistantcomposition; and (2) less than 10 percent by weight of an impactmodifier composition, based on the weight of the impact resistantcomposition, comprising; (a) less than 30 percent by weight ofhigh-density polyethylene, based on the weight of the impact modifiercomposition; and (b) at least 70 percent by weight of chlorinatedpolyethylene, based on the weight of the impact modifier composition;wherein the article has an instrumented dart drop impact of greater than0.90 inch-pounds per mil at −10° C.

In an alternative embodiment, the instant invention provides an impactmodifier composition, an impact resistant composition, method ofproducing the same, and articles made therefrom, in accordance with anyof the preceding embodiments, except that the high-density polyethyleneis in powder form.

In an alternative embodiment, the instant invention provides an impactmodifier composition, an impact resistant composition, method ofproducing the same, and articles made therefrom, in accordance with anyof the preceding embodiments, except that the chlorinated polyethyleneis in powder form.

In an alternative embodiment, the instant invention provides an impactmodifier composition, an impact resistant composition, method ofproducing the same, and articles made therefrom, in accordance with anyof the preceding embodiments, except that the impact modifiercomposition has a average particle size of less than 600 μm.

In an alternative embodiment, the instant invention provides an impactmodifier composition, an impact resistant composition, method ofproducing the same, and articles made therefrom, in accordance with anyof the preceding embodiments, except that the impact modifiercomposition has a average particle size of less than 550 μm.

In an alternative embodiment, the instant invention provides an impactmodifier composition, an impact resistant composition, method ofproducing the same, and articles made therefrom, in accordance with anyof the preceding embodiments, except that the impact modifiercomposition has a average particle size of less than 500 μm.

DETAILED DESCRIPTION OF THE INVENTION

The instant invention is an impact modifier composition, an impactresistant composition, method of producing the same, and articles madetherefrom.

The impact modifier composition comprises (a) high-density polyethylene;and (b) chlorinated polyethylene. The impact modifier composition maycomprise less than 30 percent by weight of high-density polyethylene,based on the weight of the impact modifier composition. All individualvalues and subranges from less than 30 weight percent are includedherein and disclosed herein; for example, the high-density polyethyleneweight percent may be from a lower limit of 1, 3, 5, 7, 9, 11, 13, 15,17, 19, 21, 23, 25, 27 or 29 weight percent to an upper limit of 4, 6,8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28 or 30. For example, impactmodifier composition may comprise less than 25 percent by weight ofhigh-density polyethylene, based on the weight of the impact modifiercomposition; or in the alternative, the impact modifier composition maycomprise less than 20 percent by weight of high-density polyethylene,based on the weight of the impact modifier composition. The impactmodifier composition may comprise at least 70 percent by weight of thechlorinated polyethylene, based on the weight of the impact modifiercomposition. All individual values and subranges equal or greater that70 weight percent are included herein and disclosed herein; for example,the chlorinated polyethylene weight percent may be from a lower limit of70, 75, 80, 85 or 90 weight percent to an upper limit of 75, 80, 85, 90,95, 96, 97, 98, or 99. For example, impact modifier composition maycomprise at least 75 percent by weight of chlorinated polyethylene,based on the weight of the impact modifier composition; or in thealternative, the impact modifier composition may comprise at least 80weight percent by weight of chlorinated polyethylene, based on theweight of the impact modifier composition; or in the alternative, theimpact modifier composition may comprise at least 85 weight percent byweight of chlorinated polyethylene, based on the weight of the impactmodifier composition; or in the alternative, the impact modifiercomposition may comprise at least 90 weight percent by weight ofchlorinated polyethylene, based on the weight of the impact modifiercomposition; or in the alternative, the impact modifier composition maycomprise at least 95 weight percent by weight of chlorinatedpolyethylene, based on the weight of the impact modifier composition.

The high-density polyethylene may be an ethylene homopolymer or anethylene copolymer. The high-density polyethylene may have a density inthe range of 0.940 to 0.970 g/cm³. All individual values and subrangesfrom 0.940 to 0.970 g/cm³ are included herein and disclosed herein; forexample, the density of the high-density polyethylene may be from alower limit of 0.940, 0.943, 0.945, 9.47, or 0.950 g/cm³ to an upperlimit of 0.955, 0.960, 0.963, 0.965, or 0.970 g/cm³. The high-densitypolyethylene may have a melt index (I₁₀) of less than 100 g/10 minutes.All individual values and subranges from less than 100 g/10 minutes areincluded herein and disclosed herein; for example, the melt index (I₁₀)can be from a lower limit of 0.5, 1.0, 1.5, 2.0, 5.0, 10.0, 15.0, or 20g/10 minutes to an upper limit of 0.7, 1.0, 1.5, 2.0, 2.5, 5.0, 10.0,15.0, 20, 50, or 100 g/10 minutes. For example, the high-densitypolyethylene may have a melt index (I₁₀) in the range of 0.5 to 100 g/10minutes; or in the alternative, the high-density polyethylene may have amelt index (I₁₀) in the range of 0.5 to 50 g/10 minutes; or in thealternative, the high-density polyethylene may have a melt index (I₁₀)in the range of 0.5 to 20 g/10 minutes; or in the alternative, thehigh-density polyethylene may have a melt index (I₁₀) in the range of0.5 to 10 g/10 minutes; or in the alternative, the high-densitypolyethylene may have a melt index (I₁₀) in the range of 0.5 to 2.5 g/10minutes; or in the alternative, the high-density polyethylene may have amelt index (I₁₀) in the range of 0.5 to 2.5 g/10 minutes.

The high-density polyethylene may include any amount of one or morealpha-olefin comonomers; for example, the high-density polyethylene maycomprise about less than 15 percent by weight of one or morealpha-olefin comonomers, based on the weight of the high-densitypolyethylene. All individual values and subranges less than 15 weightpercent are included herein and disclosed herein; for example, theweight percent of one or more alpha-olefin comonomers may be from alower limit of 0, 1, 2, 3, 5, 7, 9, 12, or 14 weight percent to an upperlimit of 5, 9, 10, 12, or 15 weight percent. For example, thehigh-density polyethylene may comprise about less than 10 percent byweight of one or more alpha-olefin comonomers, based on the weight ofthe high-density polyethylene; or in the alternative, the high-densitypolyethylene may comprise about less than 7 percent by weight of one ormore alpha-olefin comonomers, based on the weight of the high-densitypolyethylene; in the alternative, the high-density polyethylene maycomprise about less than 5 percent by weight of one or more alpha-olefincomonomers, based on the weight of the high-density polyethylene.

The high-density polyethylene may include any amount of ethylene; forexample, the high-density polyethylene may comprise about at least 85percent by weight of ethylene, based on the weight of the high-densitypolyethylene. All individual values and subranges equal or greater than85 weight percent are included herein and disclosed herein; for example,the weight percent of ethylene may be from a lower limit of 85, 87, 88,90, 91, 95, 98, or 99 weight percent to an upper limit of 90, 91, 93,95, 98, or 100. For example, the high-density polyethylene may compriseat least 85 percent by weight of ethylene, based on the weight of thehigh-density polyethylene; or in the alternative, the high-densitypolyethylene may comprise at least 90 percent by weight of ethylene,based on the weight of the high-density polyethylene; in thealternative, the high-density polyethylene may comprise at least 95percent by weight of ethylene, based on the weight of the high-densitypolyethylene.

The alpha-olefin comonomers typically have no more than 20 carbon atoms.For example, the alpha-olefin comonomers may preferably have 3 to 10carbon atoms, and more preferably 3 to 8 carbon atoms. Exemplaryalpha-olefin comonomers include, but are not limited to, propylene,1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene,and 4-methyl-1-pentene. The alpha-olefin comonomers may preferably beselected from the group consisting of propylene, 1-butene, 1-hexene, and1-octene, and more preferably from the group consisting of 1-hexene andI-octene.

The high-density polyethylene may be in any physical form; for example,the high density polyethylene may be pellet, micropellet, or powder. Thehigh-density polyethylene may preferably be in the powder form. Pelletsare typically defined as solid particulates with an average particlesize of 2 to 10 mm, preferably 2 to 4 mm. Micropellets are typicallydefined as solid particulates with an average particle size of 1000 μmto about 2 mm. Powders are typically defined as solid particulates withan average particle size of less than 1000 microns. The high-densitypolyethylene may have any average particle size; for example, thehigh-density polyethylene may have an average particle size in the rangeof less than 10 mm. All individual values and subranges from less than10 mm are included herein and disclosed herein; for example, thehigh-density polyethylene may have an average particle size in the rangeof less than 4 mm; or in the alternative, the high-density polyethylenemay have an average particle size in the range of 2 to 4 mm; or in thealternative, the high-density polyethylene may have an average particlesize in the range of less than 2000 μm; or in the alternative, thehigh-density polyethylene may have an average particle size in the rangeof 1000 to 2000 μm; or in the alternative, the high-density polyethylenemay have an average particle size in the range of less than 1000 μm; orin the alternative, the high-density polyethylene may have an averageparticle size in the range of less than 600 μm; or in the alternative,the high-density polyethylene may have an average particle size in therange of less than 500 μm; or in the alternative, the high-densitypolyethylene may have an average particle size in the range of less than400 μm.

Any conventional ethylene homopolymerization or copolymerizationreactions may be employed to produce the high-density polyethylenecomponent of the instant invention. Such conventional ethylenehomopolymerization or copolymerization reactions include, but are notlimited to, gas phase polymerization, slurry phase polymerization,liquid phase polymerization, and combinations thereof using conventionalreactors, e.g. gas phase reactors, loop reactors, stirred tank reactors,batch reactors, and combinations thereof in series or parallel.

The chlorinated polyethylene may be any chlorinated polyethylene. Thechlorinated polyethylene may be a chlorinated polyethylene homopolymer;or in the alternative, the chlorinated polyethylene may be a chlorinatedpolyethylene copolymer that contains copolymerized units of (a) ethyleneand (b) up to 15 weight percent of a copolymerizable monomer, based onthe weight of the polyethylene copolymer. In one embodiment, thechlorinated polyethylene is derived from a substantially linearhigh-density polyethylene homopolymer or copolymer with at least one ormore other alpha-olefin that can contain up to 10 carbon atoms, having adensity of at least 0.940 g/cm³ and having a chlorine content of fromabout 15 to about 50 percent by weight after chlorination. Suchchlorinated polyethylenes are described in U.S. Pat. No. 3,396,211,incorporated herein by reference.

The chlorinated olefin polymer may optionally contain chlorosulfonylgroups. That is, the polymer chain will have pendant chlorine groups andchlorosulfonyl groups. Such polymers are known as chlorosulfonatedolefin polymers.

Representative chlorinated and chlorosulfonated ethylene polymersinclude (a) chlorinated and chlorosulfonated homopolymers of ethyleneand (b) chlorinated and chlorosulfonated copolymers of ethylene and atleast one or more ethylenically unsaturated monomer selected from thegroup consisting of C₃ to C₁₀ alpha-olefin comonomer; C₁ to C₁₂ alkylesters of C₃ to C₂₀ monocarboxylic acids; unsaturated C₃ to C₁₀ mono- ordicarboxylic acids; anhydrides of unsaturated C₄ to C₈ dicarboxylicacids; and vinyl esters of saturated C₂ to C₁₋₈, carboxylic acids.Chlorinated and chlorosulfonated graft copolymers are included as well.Specific examples of suitable polymers include chlorinated polyethylene;chlorosulfonated polyethylene; chlorinated ethylene vinyl acetatecopolymers; chlorosulfonated ethylene vinyl acetate copolymers;chlorinated ethylene acrylic acid copolymers; chlorosulfonated ethyleneacrylic acid copolymers; chlorinated ethylene methacrylic acidcopolymers; chlorosulfonated ethylene methacrylic acid copolymers;chlorinated ethylene methyl acrylate copolymers; chlorinated ethylenemethyl methacrylate copolymers; chlorinated ethylene n-butylmethacrylate copolymers; chlorinated ethylene glycidyl methacrylatecopolymers; chlorinated graft copolymers of ethylene and maleic acidanhydride; chlorinated copolymers of ethylene with propylene, butene,3-methyl-1-pentene, or octene and chlorosulfonated copolymers ofethylene with propylene, butene, 3-methyl-1-pentene or octene. Thecopolymers may be dipolymers, terpolymers, or higher order copolymers.Preferred chlorinated olefin polymers are-chlorinated polyethylene andchlorinated copolymers of ethylene vinyl acetate.

The polyethylene base resin for the chlorinated polyethylene may anethylene homopolymer or an ethylene copolymer. The polyethylene baseresin for the chlorinated polyethylene may have a density in the rangeof 0.940 to 0.970 g/cm³. All individual values and subranges from 0.940to 0.970 g/cm³ are included herein and disclosed herein; for example,the density of the polyethylene base resin for the chlorinatedpolyethylene may be from a lower limit of 0.940, 0.943, 0.945, 9.47, or0.950 g/cm³ to an upper limit of 0.955, 0.960, 0.963, 0.965, or 0.970g/cm³. The polyethylene base resin for the chlorinated polyethylene mayhave a melt index (I₁₀) of less than 100 g/10 minutes. All individualvalues and subranges from less than 100 g/10 minutes are included hereinand disclosed herein; for example, the melt index (I₁₀) can be from alower limit of 0.05, 0.5, 1.0, 1.5, 2.0, 5.0, 10.0, 15.0, or 20 g/10minutes to an upper limit of 0.7, 0.8, 1.0, 1.5, 2.0, 2.5, 5.0, 10.0,15.0, 20, 50, or 100 g/10 minutes. For example, the polyethylene baseresin for the chlorinated polyethylene may have a melt index (I₁₀) inthe range of 0.5 to 100 g/10 minutes; or in the alternative, thepolyethylene base resin for the chlorinated polyethylene may have a meltindex (I₁₀) in the range of 0.5 to 50 g/10 minutes; or in thealternative, the polyethylene base resin for the chlorinatedpolyethylene may have a melt index (I₁₀) in the range of 0.5 to 20 g/10minutes; or in the alternative, the polyethylene base resin for thechlorinated polyethylene may have a melt index (I₁₀) in the range of 0.5to 10 g/10 minutes; or in the alternative, the polyethylene base resinfor the chlorinated polyethylene may have a melt index (I₁₀) in therange of 0.5 to 5 g/10 minutes; or in the alternative, the polyethylenebase resin for the chlorinated polyethylene may have a melt index (I₁₀)in the range of 0.5 to 2.5 g/10 minutes; or in the alternative, thepolyethylene base resin for the chlorinated polyethylene may have a meltindex (I₁₀) in the range of 0.05 to 0.8 g/10 minutes.

The chlorinated and/or chlorosulfonated ethylene polymers useful in thepractice of the instant invention may contain from 15 to 42 percent byweight of chlorine, based on the weight of the chlorinated orchlorosulfonated ethylene polymer. All individual values and subrangesfrom 15 to 42 weight percent are included herein and disclosed herein;for example, chlorinated and/or chlorosulfonated ethylene polymersuseful in the practice of the instant invention may contain from 15 to36 percent by weight of chlorine, based on the weight of the chlorinatedor chlorosulfonated ethylene polymer; or in the alternative, chlorinatedand/or chlorosulfonated ethylene polymers useful in the practice of theinstant invention may contain from 20 to 36 percent by weight ofchlorine, based on the weight of the chlorinated or chlorosulfonatedethylene polymer; or in the alternative, chlorinated and/orchlorosulfonated ethylene polymers useful in the practice of the instantinvention may contain from 20 to 30 percent by weight of chlorine, basedon the weight of the chlorinated or chlorosulfonated ethylene polymer.

If the chlorinated ethylene polymer is chlorosulfonated, it willgenerally have a sulfur content of up to 6 weight percent, preferably1-3 weight percent.

The chlorinated olefin polymers and chlorosulfonated olefin polymerssuitable for use in the impact resistant compositions of the inventionmay be prepared from polyolefin resins that are branched or unbranched.The polyolefin base resins may be prepared by free radical processes,Ziegler-Natta catalysis or catalysis with metallocene catalyst systems,for example those disclosed in U.S. Pat. Nos. 5,272,236 and 5,278,272.Chlorination or chlorosulfonation of the base resins may take place insuspension, solution, solid state or fluidized bed. Free radicalsuspension chlorination processes are described and taught in U.S. Pat.Nos. 3,454,544, 4,767,823 and references cited therein. Such processesinvolve preparation of an aqueous suspension of a finely dividedethylene polymer which is then chlorinated. An example of a free radicalsolution chlorination process is disclosed in U.S. Pat. No. 4,591,621.The polymers may also be chlorinated in the melt or fluidized beds, forexample as taught in U.S. Pat. No. 4,767,823. Chlorosulfonationprocesses are generally performed in solution but suspension andnon-solvent processes are also known. Preparation of chlorosulfonatedolefin polymers is described in U.S. Pat. Nos. 2,586,363; 3,296,222;3,299,014; and 5,242,987.

The impact modifier composition may be produced via any method. Forexample, the impact modifier composition may be produced by the physicalblending of the high-density polyethylene component and the chlorinatedpolyethylene via a method selected from the group consisting of ribbonblending, high-intensity mixing, static mixing, tumble blending, and thelike. The impact modifier composition is a physical blend and it doesnot require crosslinking or vulcanization in order to be useful ascommercial products.

The high impact resistant composition according to the instant inventioncomprises vinyl chloride polymer and impact modifier composition, asdescribed hereinabove. The high impact resistant composition accordingto instant invention may comprise at least 85 percent by weight of thevinyl chloride polymer, based on the combined weight of the vinylchloride polymer and the impact modifier composition. All individualvalues and subranges from at least 85 weight percent are included hereinand disclosed herein; for example, the high impact resistant compositionmay comprise from a lower limit of 85, 86, 87, 88, 89, 90, 92, 94, 96,98, or 99 percent by weight of the vinyl chloride polymer, based on thecombined weight of the vinyl chloride polymer and the impact modifiercomposition to an upper limit of 86, 87, 88, 89, 90, 92, 94, 96, 98, or100 percent by weight of the vinyl chloride polymer, based on thecombined weight of the vinyl chloride polymer and the impact modifiercomposition. For example, the high impact resistant composition maycomprise from 85 to 99 percent by weight of the vinyl chloride polymer,based on the combined weight of the vinyl chloride polymer and theimpact modifier composition; or in the alternative, the high impactresistant composition may comprise from 87 to 99 percent by weight ofthe vinyl chloride polymer, based on the combined weight of the vinylchloride polymer and the impact modifier composition; or in thealternative, the high impact resistant composition may comprise from 88to 99 percent by weight of the vinyl chloride polymer, based on thecombined weight of the vinyl chloride polymer and the impact modifiercomposition; or in the alternative, the high impact resistantcomposition may comprise from 90 to 99 percent by weight of the vinylchloride polymer, based on the combined weight of the vinyl chloridepolymer and the impact modifier composition. The high impact resistantcomposition according to instant invention may comprise less than 10percent by weight of the impact modifier composition, based on thecombined weight of the vinyl chloride polymer and the impact modifiercomposition. All individual values and subranges from less than 10weight percent are included herein and disclosed herein; for example,the high impact resistant composition may comprise from a lower limit of1, 2, 3, 4, 5, 6, 7, 8, or 9 percent by weight of the impact modifiercomposition, based on the combined weight of the vinyl chloride polymerand the impact modifier composition to an upper limit of 2, 3, 4, 5, 6,7, 8, 9, or 10 percent by weight of the impact modifier composition,based on the combined weight of the vinyl chloride polymer and theimpact modifier composition. For example, the high impact resistantcomposition may comprise from 1 to 10 percent by weight of the impactmodifier composition, based on the combined weight of the vinyl chloridepolymer and the impact modifier composition; or in the alternative, thehigh impact resistant composition may comprise from 1 to 8 percent byweight of the impact modifier composition, based on the combined weightof the vinyl chloride polymer and the impact modifier composition; or inthe alternative, the high impact resistant composition may comprise from1 to 6 percent by weight of the impact modifier composition, based onthe combined weight of the vinyl chloride polymer and the impactmodifier composition; or in the alternative, the high impact resistantcomposition may comprise from 1 to 5 percent by weight of the chlorideimpact modifier composition, based on the combined weight of the vinylchloride polymer and the impact modifier composition. The impactresistant composition may have any instrumented dart drop impact. Forexample, the impact resistant composition may have an instrumented dartdrop impact of greater than 0.90 inch-pounds per mil at −10° C. Allindividual values and subranges from greater than 0.90 inch-pounds permil at −10° C. are included herein and disclosed herein; for example,the impact resistant composition may have an instrumented dart dropimpact of greater than 0.91 inch-pounds per mil at −10° C.; or in thealternative, the impact resistant composition may have an instrumenteddart drop impact of greater than 0.92 inch-pounds per mil at −10° C.; orin the alternative, the impact resistant composition may have aninstrumented dart drop impact of greater than 0.95 inch-pounds per milat −10° C.; or in the alternative, the impact resistant composition mayhave an instrumented dart drop impact of greater than 1.00 inch-poundsper mil at −10° C.; or in the alternative, the impact resistantcomposition may have an instrumented dart drop impact of greater than1.20 inch-pounds per mil at −10° C.

The vinyl chloride polymer component may be any vinyl chloride polymer.For example, the vinyl chloride polymer may be a solid, high molecularweight polymer. The vinyl chloride polymer may be a polyvinyl chloridehomopolymer or a copolymer of vinyl chloride having copolymerized unitsof one or more additional comonomers. When present, such comonomers willaccount for up to 20 weight percent of the copolymer, preferably from1-10 weight percent of the copolymer, and most preferably 1-5 weightpercent of the copolymer. Examples of suitable comonomers include, butare not limited to C₂-C₁₀ olefins, for example ethylene and propylene;vinyl esters of straight chain or branched C₂-C₄ carboxylic acids, suchas vinyl acetate, vinyl propionate, and vinyl 2-ethyl hexanoate; vinylhalides, for example vinyl fluoride, vinylidene fluoride or vinylidenechloride; vinyl ethers, such as vinyl methyl ether and butyl vinylether; vinyl pyridine; unsaturated acids, for example maleic acid,fumaric acid, methacrylic acid and their mono- or diesters with C₁-C₁₀mono- or dialcohols; maleic anhydride, maleic acid imide as well as theN-substitution products of maleic acid imide with aromatic,cycloaliphatic and optionally branched aliphatic substituents;acrylonitrile and styrene. Such homopolymers and interpolymerizedcopolymers are commercially available from Georgia Gulf Corp., Atlanta,Ga., USA. They may also be prepared by any suitable polymerizationmethod. Exemplary polymers may be prepared via suspension process.

Graft copolymers of vinyl chloride are also suitable for use in theinvention. For example, ethylene copolymers, such as ethylene vinylacetate, and ethylene copolymer elastomers, such as EPDM (copolymerscomprising copolymerized units of ethylene, propylene and dienes) andEPR (copolymers comprising copolymerized units of ethylene andpropylene) that are grafted with vinyl chloride may be used as the vinylchloride polymer component.

One or more additives may further be added to the high impact resistantcomposition Exemplary additives include, but are not limited to,stabilizers, blowing agents, fillers, lubricants, colorants,crosslinking agents, process aids, and the like. Exemplary additivesinclude, but are not limited to, tin stabilizers, calcium carbonate,titanium dioxide, acrylic process aids, and hydrocarbon and ester waxes.Up to 50 parts by weight of one or more additives per 100 parts of thehigh impact resistant composition may be added to the high impactcomposition. All individual values and subranges from up to 50 parts per100 parts of the high impact resistant composition are included hereinand disclosed herein; for example, one or more additives may be presentfrom a lower limit of 0.1, 0.5, 1, 5, 10, 15, 20, 30, 35, 40, 45, or 49parts per 100 parts of the high impact resistant composition to an upperlimit of 1, 5, 10, 15, 20, 30, 35, 40, 45, or 50 parts per 100 parts ofthe high impact resistant composition. For example, from 0.1 to 50 partsby weight of one or more additives per 100 parts of the high impactresistant composition may be added to the high impact composition; or inthe alternative, from 0.5 to 40 parts by weight of one or more additivesper 100 parts of the high impact resistant composition may be added tothe high impact composition; or in the alternative, from 1 to 30 partsby weight of one or more additives per 100 parts of the high impactresistant composition may be added to the high impact composition; or inthe alternative, from 5 to 25 parts by weight of one or more additivesper 100 parts of the high impact resistant composition may be added tothe high impact composition; or in the alternative, from 10 to 25 partsby weight of one or more additives per 100 parts of the high impactresistant composition may be added to the high impact composition; or inthe alternative, from 15 to 25 parts by weight of one or more additivesper 100 parts of the high impact resistant composition may be added tothe high impact composition; or in the alternative, from 15 to 20 partsby weight of one or more additives per 100 parts of the high impactresistant composition may be added to the high impact composition.

One or more polymers may further be added to the high impact resistantcomposition. Such one or more polymers include, but are not limited to,acrylonitrile butadiene styrene copolymers (ABS), methacrylate butadienestyrene copolymers, (MBS), modified acrylic polymers.

The method for producing the impact resistant composition comprises thesteps of (I) selecting poly(vinyl chloride); (2) selecting an impactmodifier composition comprising; (a) less than 30 percent by weight ofhigh-density polyethylene, based on the weight of impact modifiercomposition; and (b) at least 70 percent by weight of chlorinatedpolyethylene, based on the weight of impact modifier composition; (3)melt blending the poly(vinyl chloride) and the impact modifiercomposition; and (4) thereby producing the impact resistant compositioncomprising at least 85 percent by weight of poly(vinyl chloride), basedon the weight of the impact resistant composition; and (2) less than 10percent by weight of the impact modifier composition. In an exemplaryprocess for producing the impact resistant composition of the instantinvention, the vinyl chloride polymer component in a powder form and theimpact modifier composition in the powder form are fed into an extruder,e.g. single screw extruder or twin screw extruder, and melt blended intoa substantially homogenous mixture at melt temperatures in the range of150° C. to 220° C. All individual values and subranges from 150° C. to220° C. are included herein and disclosed herein; for example, the melttemperature may be from a lower limit of 150, 155, 160, 165, 170, 175,180, 185, 190, 195, 200, 210, 215° C. to an upper limit of 155, 160,165, 170, 175, 180, 185, 190, 195, 200, 210, 215, or 220° C. Forexample, the melt temperature may be in the range of 160 to 215° C., orin the alternative, the melt temperature may be in the range of 160 to210° C., or in the alternative, the melt temperature may be in the rangeof 160 to 205° C., or in the alternative, the melt temperature may be inthe range of 160 to 200° C., or in the alternative, the melt temperaturemay be in the range of 160 to 195° C., or in the alternative, the melttemperature may be in the range of 160 to 190° C. The high impactresistant compositions according to the instant invention are physicalblends and do not require crosslinking or vulcanization.

The articles according to the instant invention comprise (1) at least 85percent by weight of poly(vinyl chloride), based on the weight of theimpact resistant composition; and (2) less than 10 percent by weight ofan impact modifier composition, based on the weight of the impactresistant composition, comprising; (a) less than 30 percent by weight ofhigh-density polyethylene, based on the weight of impact modifiercomposition; and (b) at least 70 percent by weight of chlorinatedpolyethylene, based on the weight of impact modifier composition;wherein the article has an instrumented dart drop impact of greater than0.90 inch-pounds per mil at −10° C. Such articles include, but are notlimited to, rigid PVC articles, PVC sidings, PVC window profiles, PVCpipes, fences, decks, conduits and like. The articles according toinstant invention may have any instrumented dart drop impact. Forexample, the articles according to instant invention may have aninstrumented dart drop impact of greater than 0.90 inch-pounds per milat −10° C. All individual values and subranges from greater than 0.85inch-pounds per mil at −10° C. are included herein and disclosed herein;for example, the articles may have an instrumented dart drop impact ofgreater than 0.91 inch-pounds per mil at −10° C.; or in the alternative,the articles may have an instrumented dart drop impact of greater than0.92 inch-pounds per mil at −10° C.; or in the alternative, the articlesmay have an instrumented dart drop impact of greater than 0.95inch-pounds per mil at −10° C.; or in the alternative, the articles mayhave an instrumented dart drop impact of greater than 1.00 inch-poundsper mil at −10° C.; or in the alternative, the articles may have aninstrumented dart drop impact of greater than 1.20 inch-pounds per milat −10° C.

EXAMPLES

The following examples illustrate the present invention but are notintended to limit the scope of the invention. The examples of theinstant invention demonstrate that the high impact compositionsaccording to instant invention possess improved low temperature impactproperties at optimum efficiency.

Inventive samples 1-3 and comparatives 1-7 were prepared according tothe following process. The formulations for inventive samples 1-3 andcomparative samples 1-7 are shown in Tables I and II. TYRIN™ 2500P is achlorinated polyethylene (˜25% chlorine content), commercially availablefrom The Chemical Company, Midland, Mich., USA. SHINTECH 950 is a vinylchloride polymer, commercially available from Shintech, Inc., Houston,USA. HDPE-1 is a high-density polyethylene, which was provided by TheDow Chemical Company, having a density of 0.965 g/cc, and melt index(I₁₀) of 95 g/10 minutes. HDPE-2 is a high-density polyethylene, whichwas provided by The Dow Chemical Company, having a density of 0.965, andmelt index (I₁₀) of 2.3 g/10 minutes. HDPE-3 is a high-densitypolyethylene, which was provided by The Dow Chemical Company, having adensity of 0.965, and melt index (I₁₀) of 0.5 g/10 minutes. Theformulation components for inventive samples 1-3 and comparative samples1-7, as shown in Tables I and II, were mixed in a high intensity Littleford blender, and the blend was extruded via a Cincinnati Milacron CM-55conical twin screw extruder attached to a sheet die at a motor load ofapproximately 43-45 amps, and a IR temperature of approximately 380-385°F. The samples were tested for instrumented dart drop impact accordingto ASTM D-3763-02, and the results are shown in Table III.

TEST METHODS

Test Methods Include the Following:

The instrumented dart drop impact was determined according to ASTMD-3763-02 (Dynatup Impact @−10° C.).

Density was measured according to ASTM D 792-03, Method B, inisopropanol.

Melt index (I₁₀) was measured at 190° C. under a load of 10.0 kgaccording to ASTM D-1238-03.

Average Particle Size was determined via Beckman Coulter LS 13 320 LaserDiffraction Particle Size Analyzer.

The present invention may be embodied in other forms without departingfrom the spirit and the essential attributes thereof, and, accordingly,reference should be made to the appended claims, rather than to theforegoing specification, as indicating the scope of the invention.

TABLE I Formulation Components Units Inventive 1 Inventive 2 Inventive 3SHINTECH 950 (PVC) Parts 100 100 100 TYRIN 2500P Parts 3.2 3.2 3.2HDPE-1 Parts 0.8 — — HDPE-2 Parts — 0.8 — HDPE-3 Parts — — 0.8 OMYACRABUFT (Calcium Carbonate) Parts 12 12 12 STEARIC ACID Parts 0.25 0.25 0.25AC 629A (Oxidized PE Wax) Parts 0.15 0.15 0.15 CALCIUM STEARATE Parts0.8 0.8 0.8 PARALOID K-120N (Acrylic Process Aid) Parts 1.0 1.0 1.0HOSTALUB XL165 (Paraffin Wax) Parts 1.5 1.5 1.5 ADVASTAB TM-286 (MethylTin Stabilizer) Parts 1.0 1.0 1.0 TI-PURE R960 (Titanium Dioxide) Parts0.5 0.5 0.5 Total Parts Parts 121.2 121.2 121.2

TABLE II Comparative Comparative Comparative Comparative ComparativeFormulation Components Units 1 2 3 4 5 Comparative 6 Comparative 7SHINTECH 950 (PVC) Parts 100 100 100 100 100 100 100 TYRIN 2500P Parts4.0 2.0 0.8 2.64 2.0 2.64 2.0 HDPE-1 Parts — 2.0 3.2 — — — — HDPE-2Parts — — — 1.36 2.0 — — HDPE-3 Parts — — — — — 1.36 2.0 OMYACRAB UFT(Calcium Parts 12 12 12 12 12 12 12 Carbonate) STEARIC ACID Parts 0.250.25 0.25 0.25 0.25 0.25 0.25 AC 629A (Oxidized PE Wax) Parts 0.15 0.150.15 0.15 0.15 0.15 0.15 CALCIUM STEARATE Parts 0.8 0.8 0.8 0.8 0.8 0.80.8 PARALOID K-120N (Acrylic Parts 1.0 1.0 1.0 1.0 1.0 1.0 1.0 ProcessAid) HOSTALUB XL165 (Paraffin Wax) Parts 1.5 1.5 1.5 1.5 1.5 1.5 1.5ADVASTAB TM-286 (Methyl Tin Parts 1.0 1.0 1.0 1.0 1.0 1.0 1.0Stabilizer) TI-PURE R960 (Titanium Dioxide) Parts 0.5 0.5 0.5 0.5 0.50.5 0.5 Total Parts Parts 121.2 121.2 121.2 121.2 121.2 121.2 121.2

TABLE III Instrumented Dart Drop Impact (Dynatup Impact @ −10° C.)Inventive 1 1.43 Inventive 2 1.25 Inventive 3 1.68 Comparative 1 0.89Comparative 2 0.24 Comparative 3 0.03 Comparative 4 0.82 Comparative 50.37 Comparative 6 0.56 Comparative 7 0.64

1. An impact modifier composition comprising: less than 30 percent byweight of high-density polyethylene based on the total weight of theimpact modifier composition; at least 70 percent by weight ofchlorinated polyethylene.
 2. The impact modifier of claim 1, whereinsaid high-density polyethylene is in the powder form.
 3. The impactmodifier of claim 1, wherein said chlorinated polyethylene is in thepowder form.
 4. An impact resistant composition comprising the meltblending product of: at least 85 percent by weight of vinyl chloridepolymer; less than 10 percent by weight of an impact modifiercomposition comprising; less than 30 percent by weight of high-densitypolyethylene based on the total weight of the impact modifiercomposition; at least 70 percent by weight of chlorinated polyethylene.5. The impact resistant composition of claim 4, wherein said vinylchloride polymer is in the powder form.
 6. The impact resistantcomposition of claim 4, wherein said high-density polyethylene is in thepowder form.
 7. The impact resistant composition of claim 4, whereinsaid chlorinated polyethylene is in the powder form.
 8. An impactresistant composition comprising: at least 85 percent by weight of unitsderived from vinyl chloride polymer; less than 10 percent by weight ofunits derived from an impact modifier composition comprising; less than30 percent by weight of high-density polyethylene based on the totalweight of the impact modifier composition; at least 70 percent by weightof chlorinated polyethylene.
 9. The impact resistant composition ofclaim 8, wherein said impact resistant composition has a instrumenteddart drop impact of greater than 0.90 inch-pounds per mil at −10° C. 10.A method of producing an impact modifier composition comprising thesteps of: selecting high-density polyethylene in a powder form;selecting chlorinated polyethylene in a powder form; uniformly admixingsaid high-density polyethylene and said chlorinated polyethylene;thereby producing said impact modifier composition.
 11. An articlecomprising: at least 85 percent by weight of units derived from vinylchloride polymer; less than 10 percent by weight of units derived froman impact modifier composition comprising; less than 30 percent byweight of high-density polyethylene based on the total weight of theimpact modifier composition; at least 70 percent by weight ofchlorinated polyethylene; wherein said article has a instrumented dartdrop impact of greater than 0.90 inch-pounds per mil at −10° C.
 12. Thearticle according to claim 11, wherein said article is a pipe, siding,window profile, door profile, decking, railing, conduit, and the like.13. The article according to claim 11, wherein said article has ainstrumented dart drop impact of greater than 0.90 inch-pounds per milat −10° C.